There are today clear indications that the Li-ion battery of the type currently used worldwide in mobile-phones and lap-tops is also destined to soon become the battery of choice in more energy-demanding concepts such as electric and electric hybrid vehicles (EVs and EHVs). Since the currently used cathode materials (typically of the Li(Ni,Co)O2-type) are too expensive in large-scale applications, these new batteries will have to exploit some much cheaper transition-metal. Ideally, this should be the very cheapest - iron(Fe) - in combination with a graphite(C)-based anode. In this context, the obvious Fe-based active cathode of choice appears to be LiFePO4. A second and in some ways even more attractive material - Li2FeSiO4 - has emerged during the course of this work. An effort has here been made to understand the Li extraction/insertion mechanism on electrochemical cycling of Li2FeSiO4. A fascinating picture has emerged (following a complex combination of Mössbauer, X-ray diffraction and electrochemical studies) in which the material is seen to cycle between Li2FeSiO4 and LiFeSiO4, but with the structure of the original Li2FeSiO4 transforming from a metastable short-range ordered solid-solution into a more stable long-range ordered structure during the first cycle. Density Functional Theory calculations on Li2FeSiO4 and the delithiated on LiFeSiO4 structure provide an interesting insight into the experimental result. Photoelectron spectroscopy was used to study the surface chemistry of both carbon-treated LiFePO4 and Li2FeSiO4 after electrochemical cycling. The surface-layer on both materials was concluded to be very thin and with incomplete coverage, giving the promise of good long-term cycling. LiFePO4 and Li2FeSiO4 should both be seen as highly promising candidates as positive-electrode materials for large-scale Li-ion battery applications.

Thin metal films have found their use in many magnetic devices. They form pseudo two-dimensional systems, where the mechanisms for the magnetic interactions between the layers are not completely understood. Layered crystal structures have an advantage over such artificial systems, since the layers can be strictly mono-atomic without any unwanted admixture. In this study, some model systems of layered magnetic crystal structures and their solid solutions have been investigated by x-ray and neutron diffraction, Mössbauer and electron spectroscopy, heat-capacity and magnetic measurements, and first-principle electronic structure calculations, with the goal of deepening our understanding through controlled chemical synthesis. The compounds TlCo2S2, TlCo2Se2 and their solid solution TlCo2Se2-xSx, all containing well separated cobalt atom sheets, order with the moments ferromagnetically aligned within the sheets. In TlCo2S2, the net result is ferromagnetism, while TlCo2Se2 exhibits antiferromagnetism. The inter-layer distance is crucial for the long-range coupling, and it was varied systematically through Se-S substitution. The incommensurate helical magnetic structure found for TlCo2Se2 (x = 0) prevails in the composition range 0 ≤ x ≤ 1.5 but the pitch of the helix changes. The accompanying reduction in inter-layer distance on sulphur substitution varies almost linearly with the coupling angle of the helix. An additional competing commensurate helix (90°) appears in the medium composition range (found for x = 0.5 and 1.0). The systems TlCo2-xMexSe2 show helical magnetic ordering for Me = Fe or Cu, while a collinear antiferromagnetic structure occurs for Me = Ni. Magnetic order is created by iron substitution for copper in the Pauli paramagnetic TlCu2Se2, but now with the moments perpendicular to the metal sheets. TlCrTe2 forms a quite different crystal structure, with intra-layer ferromagnetic alignment and net collinear antiferromagnetism. In contrast to the other phases, the values of the moments conform well to a localised model for Cr3+.

The solid state, hydrothermal and flux methods were used for the investigation of alkaline earth and transition metal borophosphate compounds. The products and the phase relations were investigated by XRD, IR, DTA, and EDX methods. The solid state reactions of several boron compounds with different phosphating agents have been studied in the temperature range of 400-1200 oC. Hydrothermal and flux techniques were performed at 150 oC and 1200 oC, respectively. On the other hand, an attempt has been made to prepare a novel borophosphate compound MIIMIV[BPO7] (where MIV= Zr4+, Si4+, and MII= Sr2+, Ca2+) by solid state reactions and to investigate intermediate and final products. (NH4)2HPO4 and NH4H2PO4 were used as a phosphating agent. For the synthesis of these new compounds, the following reaction was predicted using the stoichiometric amount of the reactants: 2MIVO2 + 2MIICO3 + B2O3 + 2(NH4)2HPO4 &amp / #8594 / 2MIIO.MIVO2.B2O3.P2O5 + 4NH3 + 3H2O + 2CO2 (According to IUPAC formulation for the compounds composed of oxides) In the case of MIV=Zr4+ and MII=Sr2+, the formation of ZrSr[BPO7] was observed together with ZrO2 and SrBPO5. The formation of a new phase was proved by indexing the XRD pattern of the product after separating ZrO2 and SrBPO5 lines. Its crystal system was found to be orthorhombic and the unit cell parameters are a=11.85&Aring / , b=12.99 &Aring / , c=17.32 &Aring / . IR analysis shows that there is [BPO7]6- bands in the spectrum. At higher temperatures, Sr7Zr(PO4)6 was obtained. In the case of MIV=Si4+, SrBPO5 was the main product together with unreacted SiO2. At 1100 oC, Si4+ entered SrBPO5 structure and the product was indexed in orthorhombic system with a=8.9243 &Aring / , b=13.1548 &Aring / , and c=5.4036 &Aring / . Several other M:B:P ratios were tried for solid state systems. For compositions with different cations (such as Al3+, Ca2+, Na+), reactions generally pass through metal phosphates and BPO4. The X-ray diffraction powder pattern and infrared spectrum of several intermediate products obtained at different temperatures were presented and the several phase relations were investigated. The DTA and EDX analyses of some products were also reported.

In this study some of the first row transition metal oxides were transformed to metal sulfides by new solid gas reaction system. Transition metal sulfides have wide application area in industry and technology. Several techniques are known for the production of metal sulfides. Such as reactions between metal or metal oxide with H2S, precipitation in several liquid medium, reaction between metal and sulfur in closed vessel, chemical vapor deposition (CVD) technique. These techniques will have some disadvantages / for example, reactants are rarely available or expensive materials, their production systems are complicated and hard to set up these systems, products contain oxygen or hydrogen or corresponding metal sulfate as impurities. In our new sulfidizing system the reactants are metal oxides, carbon and SO2. These materials can be found easily. Especially, SO2 usage in this system is a big advantage of giving possibility of usage the hazardous waste product of SO2 in industry. The sulfidizing gas mixture was obtained by passing SO2 over activated carbon at 750 OC in a vertical tubular furnace. The obtained gas contains, mainly, CS2, CO and COS. The sulfidizing reactions took place in the horizontal tubular furnace at 450OC-1250 OC. The duration of the reaction, (three hours), and flow rate (60ml/min) of the SO2 gas were kept constant. The products were examined by X-ray powder diffraction and Raman scattering spectroscopy. All examined metal oxides were transformed to metal sulfides by sulfidizing gas mixture successfully. Ti3S5 was obtained from TiO2. Cr2S3 was obtained from Cr2O3. MnS (Alabandite) was obtained from MnO2. FeS and Fe1-xS (Pyrrhotite) were obtained from Fe2O3. Co9S8 (Cobaltpentlandite) and CoS (Jaipurite) were obtained from Co3O4. NiS was obtained from NiO. Cu7.2S, Cu1.6S (Calcocite-Q), Cu1.81S, Cu7S4 (Anilite) Cu9S5 (Digenite), Cu8S5 (Geerite) were obtained from CuO, ZnS was obtained from ZnO. The electrical conductivity character of each product obtained by sulfidizing reaction was analyzed in the temperature range of 77 K-300 K. Titanium sulfide, cobalt sulfide and nickel sulfide showed metallic conductivity, cupper sulfide and iron sulfide showed semiconductor behavior in this temperature range.

Orientador: Prof. Dr. Fabio Furlan Ferreira / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / Atualmente, o câncer é um dos problemas de saúde pública mais complexos que o sistema de saúde brasileiro enfrenta, dada a sua magnitude epidemiológica, social e econômica. É bem sabido que a combretastatina A4 (CA-4), que é isolada a partir das cascas da árvore sul-africana, cujo nome científico é Combrettum caffrum, é utilizada para inibir a angiogênese, que consiste no crescimento de novos vasos sanguíneos a partir dos já existentes. No entanto, dependendo da dose administrada ao paciente, a CA-4 pode causar alguns efeitos colaterais. Aqui, será apresentada a caracterização físico-química de um novo derivado N-acilidrazônico - LASSBio-1735 - um análogo da CA-4. O LASSBio-1735 foi avaliado quanto a seus efeitos citotóxicos, por ensaios de MTT, frente às linhagens tumorais HL-60 (leucemia humana), SF-295 (glioblastoma humano), MDA-MB435 (melanoma) e HCT-8 (carcinoma ileocecal ¿ cólon), apresentando resultados promissores. Pudemos determinar com êxito as estruturas cristalinas - utilizando dados de difração de raios X por policristais e um procedimento de simulated annealing - das formas anidra e di-hidratada do composto sintetizado. Foi observado que os compostos cristalizaram em sistemas cristalinos ortorrômbicos, porém em distintos grupos espaciais. A forma anidra cristalizou no grupo espacial Pna21 e a forma hidratada no grupo espacial P212121. Os efeitos sobre a viabilidade celular das formas anidra e di-hidratada do LASSBio-1735 foram comparativamente avaliados em diferentes linhagens tumorais e a forma di-hidratada exibiu maior citotoxicidade frente a linhagem tumoral K562 (leucemia mieloide crônica). Os resultados de velocidade de dissolução intrínseca levaram-nos a classificar o LASSBio-1735 em suas diferentes formas como um fármaco de baixa solubilidade, tendo sido observado um ligeiro aumento da solubilidade da forma anidra quando comparada a forma di-hidratada. / Currently, cancer is one of the most complex public health problems faced by the Brazilian health system, given its epidemiological, social and economic magnitudes. It is well known that combretastatin A4 (CA-4), which is isolated from Combretum caffrum, is used to inhibit angiogenesis, which is related to the growth of new blood vessels from the existing ones. However, depending on the dose administered to the patient, it can cause some side-effects. Herein, we present the physicochemical characterization of a novel N-acylhydrazone derivative ¿ LASSBio-1735 ¿ a CA-4 analogue. LASSBio-1735 was evaluated for its cytotoxic effects, using MTT assays, against HL-60 (human leukemia), SF-295 (human glioblastoma), MDA-MB435 (melanoma) and HCT-8 (ileocecal adenocarcinoma) tumor cells, showing promising results. We could successfully determine the crystal structures ¿ by using X-ray powder diffraction data and a simulated annealing procedure ¿ of the anhydrous and hydrated forms of the as-synthesized compound. Both compounds crystallized in orthorhombic crystal systems but under different space groups. The anhydrous form crystallized in the Pna21 while the hydrated one in the P212121 space groups. The effects on cell viability of anhydrous and dihydrated forms of LASSBio-1735 were comparatively evaluated in different tumor cell lines, and the dihydrated form exhibited higher cytotoxicity against the K562 (human chronic myeloid leukemia) tumor cell line. The results of intrinsic dissolution rate lead us to classify LASSBio-1735 in its different forms as a pharmaceutical candidate with low solubility; however, a slight solubility increase of the anhydrous form when compared to the dihydrated one was found.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-07-11T20:01:58Z No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-13T16:38:18Z (GMT) No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) / Made available in DSpace on 2016-07-13T16:38:18Z (GMT). No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) Previous issue date: 2012-02-27 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A hipertensão arterial é uma doença que acomete milhões de pessoas no mundo todo, por esse motivo a classe de médicos cardiologistas na publicação da V Diretrizes Brasileiras de Hipertensão Arterial ressaltou a importância de não se obter medicamentos anti-hipertensivos via farmácias de manipulação. De acordo com o que foi discutido, isso se deve a inexistência de informações adequadas de controle de qualidade, bioequivalência e/ou interação química dos compostos. Os fármacos utilizados no tratamento da hipertensão são administrados oralmente na forma sólida, podendo, portanto, cristalizar-se em diversas formas cristalinas, fenômeno este conhecido como polimorfismo. O polimorfismo em fármacos é um tema de grande interesse para a comunidade cientifica e apresenta um grande desafio para as indústrias farmacêuticas, uma vez que alterações no arranjo cristalino podem alterar as propriedades físico-químicas dos fármacos, e consequentemente afetar o desenvolvimento, a segurança e a eficácia de um medicamento. A principal técnica de caracterização do polimorfismo é a difração de raios X, cuja principal vantagem em relação às outras técnicas consiste na habilidade de diferenciar de maneira inequívoca uma fase cristalina da outra, mesmo que essa possua a mesma composição. Devido a todos os pontos levantados, nesse trabalho realizou-se a identificação e a quantificação de fases cristalinas dos fármacos anti-hipertensivos, Losartana, Clortalidona e Hidroclorotiazida que são disponibilizados às farmácias de manipulação da cidade de Juiz de Fora, denominadas de A e B. Realizou-se também a quantificação de fases em associações dos mesmos. Para esses propósitos as técnicas utilizadas foram espectroscopia vibracional Raman, análise termogravimétrica (TG) e calorimetria exploratória diferencial (DSC), análise elementar de carbono, hidrogênio, nitrogênio e a difração de raios X por policristais. Os resultados mostraram que para os diuréticos (Clortalidona e Hidroclorotiazida) apenas uma fase cristalina foi encontrada nas amostras, porém para a Losartana foram observadas as fases ortorrômbica e monoclínica. A análise de fases indicou que a técnica pode ser utilizada na quantificação de associação de medicamentos. / Hypertension is one of the most prevalent diseases worldwide affecting millions of people, for this reason the cardiologists in the publication of the V Brazilian Guidelines on Hypertension emphasized the importance of not buying antihypertensive medications through manipulation pharmacies. According to what was discussed, this is due to a lack of adequate information quality control, bioequivalence and / or chemical interaction of the compounds. The drugs used to treat hypertension are administered orally in solid form and therefore can crystallize in different crystalline forms, a phenomenon known as polymorphism. Polymorphism in drugs is a topic of great interest to the scientific community and presents a great challenge for the pharmaceutical industry, since changes in the crystalline arrangement can change the physicochemical properties of drugs, and consequently affect the development, security and effectiveness of a drug. The main technique for polymorphism characterization is the X-ray diffraction, whose main advantage over other techniques is the ability to differentiate unequivocally one of the other crystalline phases, even though this has the same composition. Based on aforementioned points, in this work was carried out the identification and quantification of crystalline phases of antihypertensive drugs, Losartan, Hydrochlorothiazide and Chlorthalidone that are available to manipulation pharmacies in Juiz de Fora city, named A and B. There was also the quantification of phases in the same associations. For these purposes the techniques used were Raman vibrational spectroscopy, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC), elemental analysis of carbon, hydrogen and nitrogen, and X-ray powder diffraction. The results showed that for diuretics (Hydrochlorothiazide and Chlorthalidone) only one crystalline phase was found in the samples, but for Losartan were observed orthorhombic and monoclinic phases. The phase analysis indicated that this technique can be used in quantifying drug combination.

Cette thèse participe au développement d’un combustible particulaire uranium-molybdène dans le cadre de la conversion des réacteurs de recherche de haute-performance en France et à travers le monde, à l’utilisation de combustibles faiblement enrichis (LEU : Low Enriched Uranium à opposer à HEU : High Enriched Uranium). Ce dernier se présente sous la forme d’une dispersion de particules uranifères U(Mo) dans une matrice à base d’aluminium et une question majeure persiste quant à l’interaction se produisant entre le composé U(Mo) et la matrice d’aluminium. En effet, il a été constaté que sous certaines conditions d’irradiation, cette interaction donne lieu à un gonflement instable de la plaque combustible qui résulte d’une percolation accentuée et imprévisible de bulles de gaz de fission à l’interface entre une couche d’interaction formée autour des particules U(Mo) et la matrice aluminium. Cette thèse s’est attachée à développer plusieurs solutions « remèdes » visant à modifier et/ou diminuer, voire inhiber l’interaction combustible/matrice et à améliorer la rétention des bulles de gaz de fission. Pour atteindre ces objectifs, deux voies ont été testées au cours de la thèse, (i) l’amélioration des propriétés microstructurales intrinsèques de l’alliage U(Mo) et (ii) la modification de l’interface âme combustible / matrice, par le dépôt de couches à effet barrière. En ce qui concerne le premier axe de recherche, une campagne de caractérisation des poudres de référence a, au préalable, été réalisée, permettant d’identifier des paramètres clés pour le développement de produits à microstructure « optimisée ». Deux produits innovants ont ainsi été développés puis soumis à caractérisation : une poudre atomisée-broyée et une poudre obtenue par magnésiothermie. Nous avons démontré que ces produits peuvent être un atout vis-à-vis de la problématique de rétention des bulles de gaz de fission. En ce qui concerne la problématique de la formation d’une couche d’interaction, un troisième produit, reposant sur le génie des procédés, a été développé : une poudre U(Mo) atomisée, revêtue d’une couche type alumine. Nous avons démontré qu’une couche comprise entre 100 et 200 nm permettait d’inhiber la croissance d’une couche d’interaction activée thermiquement. Nos recommandations finales ont ainsi pu être données en vue de la réalisation de tests d’irradiation « en-pile » pour la qualification d’un combustible U(Mo) optimisé. / This thesis enters in the Material and Testing Reactors (MTRs) framework where the necessity to use a Low-Enriched Uranium (LEU) fuel has led to the development of a dense fissile material based on U(Mo) alloys. The designed fuel is a composite material, made of dispersed U(Mo) particles embedded in an Al based matrix. Post-Irradiation Examinations of these LEU fuel plates showed that the irradiation behaviour of the fuel is not fit for purpose yet. This is mainly due to the growth of an interaction layer between the fuel and the matrix and to the bad gas retention efficiency of the fuel particles. This thesis had for purpose the development of several solutions in order to modify and/or decrease or even inhibit the fuel/matrix interaction and to increase the gas retention capacities of the fuel. In order to achieve so, two solutions have been tested during this thesis, (i) optimization of the U(Mo) alloy intrinsic microstructural properties and (ii) modificationof the fuel meat/matrix interface, through the deposition of a layer acting as a ''diffusion barrier''. Concerning the first axe of study, a characterization campaign of the reference powders has been realized, as a first step, in order to identify the key parameters for the development of products showing an “optimized” microstructure. Two novel products have then been developed: one based on a combined process associating “atomization + grinding” and another, which consists in a magnesiothermy process. These products were subject to characterization: X-Ray and neutron diffraction, electron backscattered diffraction and transmission electron microscopy have been performed in particular. We managed to show that these powders can be an advantage concerning the issue with the gas retention capacities of the fuel. Concerning the growth of the interaction layer, a third product, using process engineering, has been developed: an U(Mo) atomized powder, coated with an alumina like layer. We managed to show that a thickness between 100 and 200 nm of the layer allowed inhibiting the growth of a thermally activated interaction layer. Finally, our recommendations have been given in order to realize irradiation tests “in-pile” for the qualification of an optimized U(Mo) fuel.

Im Rahmen dieser Arbeit wurden neuartige, gemischte Tetrahydridoborate (Borhydride), die für die Wasserstoffspeicherung im Festkörper für die mobile Anwendung geeignet sein könnten, synthetisiert und vollständig charakterisiert. Entscheidende Materialanforderungen für die Kombination mit einer Tieftemperaturbrennstoffzelle sind die hohe Wasserstoffspeicherkapazität von min. 6 m% bei einer Wasserstoffdesorption unterhalb von 100°C. Um beide dieser Hauptkriterien zu erfüllen, wurden Li-Al- und Na-Al-Borhydrid entsprechend dem Konzept von Nakamori u.a. ausgewählt. Beide Borhydride desorbieren unterhalb von 100°C, wobei das synthetisierte Li-Al-Borhydrid aufgrund des hohen Wasserstoffgehalts (17,2 m% H2) die vielversprechendsten Eigenschaften zeigte. Beide Systeme wurden mittels Pulverdiffraktometrie am Synchrotron hinsichtlich Ihrer Struktur aufgeklärt, wobei die Struktur der einzelnen komplexen Ionen anhand von Schwingungsspektroskopie (Infrarot-, Ramanspektroskopie) ebenfalls bestätigt werden konnte. Mit Hilfe verschiedener kombinierter Desorptionsanalysen war es möglich den Zersetzungspfad, insbesondere die Bildung instabiler Desorptionsprodukte, aufzuklären. So erfolgt die Zersetzung des Li-Al-Borhydrids über die Bildung von Lithiumborhydrid in der Festphase, das mittels in-situ Ramanspektroskopie in einer speziellen Ramanzelle beobachtet werden konnte. Die Infrarotspektroskopie des Desorptionsgases zeigte zunächst die Freisetzung von Aluminiumborhydrid, dass wiederrum Diboran und Wasserstoff desorbiert. Weiterhin wurden verschiedene Möglichkeiten verfolgt, wie der Zusatz von Kohlenstoff oder das Nanoconfinement von Lithiumalanat, um den Zersetzungsweg hinsichtlich ausschließlicher Wasserstofffreisetzung zu modifizieren und somit Reversibilität zu ermöglichen. Es konnte jedoch kein reversibles System mit hoher gravimetrischer Wasserstoffspeicherdichte und Desorption unterhalb von 100°C erzeugt werden. / Aim of the work was the synthesis and characterisation of novel mixed tetrahydroborates (borohydrides) for solid state hydrogen storage suitable for mobile applications. The combination with a PEM fuel cell requires a material with at least 6 wt% hydrogen combined with hydrogen desorption below 100°C. To fulfill both criteria, Li-Al- und Na-Al-borohydride were selected according to Nakamori’s concept. Both mixed borohydrides desorb well below 100°C whereas the mixed Li-Al-borohydride showed the most promising properties due to its high gravimetric hydrogen content (17.2 wt% H2). The crystal structures were examined by powder diffraction with a synchrotron source. The symmetry of the containing complex cations and anions was confirmed with vibrational spectroscopy (infrared, raman spectroscopy). The desorption pathway was clarified using a variety of combined thermal analysis techniques. Especially the desorption of unstable products of the most promising Li-Al-borohydride was possible via spectroscopy. Hence the desorption of Li-Al-borohydride leads to the formation of lithium borohydride in the solid state which was monitored via in-situ raman spectroscopy in a special raman cell. Infrared spectroscopy of the desorbed gas showed the initial desorption of aluminium borohydride which desorbs diborane and hydrogen in the following. Different options were examined in order to modify this desorption pathway by carbon addition or nanoconfinement of lithium alanate. However, none of the materials showed high hydrogen content combined with exclusive hydrogen desorption below 100°C and reversibility.

Die Hydrierung von Zintl-Phasen führt zur Bildung von Einlagerungshydriden, die ausschließlich von Kationen koordiniert sind, zu polyanionischen Hydriden, bei denen Wasserstoff kovalent an das stärker elektronegative Element bindet, oder zu einer Kombination von beiden Motiven. Es wurde eine Reihe neuer Verbindungen dargestellt und mittels Laborröntgen-, Synchrotron- und Neutronenpulverbeugung strukturell charakterisiert. Die meisten Beispiele werden durch die Hydrierung von Zintl-Phasen im CrB- oder FeB-Strukturtyp erhalten. Die beiden Typen sind strukturell eng verwandt. Sie sind durch das Auftreten von polyanionischen Zickzackketten gekennzeichnet. Die Einlagerungshydride LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) sind Oxidationsprodukte der formal metallischen Zintl-Phasen LnTt = Ln3+ Tt2- e- . Wasserstoff besetzt dabei Ln-Tetraederlücken. Die Produkte treten als gefüllter FeB- (P -Phase, LaGeH-Strukturtyp) oder als gefüllter CrB-Strukturtyp (C -Phase, NiZrH-Strukturtyp) auf. Die Hydrierung der elektronenpräzisen Zintl-Phasen AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-Strukturtyp) führt zu wasserstoffarmen (AeTtHy , y < 1) und wasserstoffreichen (AeTtHy , 1 < y ≤ 2) Phasen. Erstere weisen partiell gefüllte Ae4-Lücken auf. In Phasen mit kleinem y (< 0.4) wird der Wasserstoff statistisch über die Lücken verteilt (α-Phasen). Etwas höhere Gehalte führen zu partieller (β-SrGeHy , 0.47 < y < 0.75) oder vollständiger (β-BaGeH0.5 ) Ordnung. Die wasserstoffreichen Phasen AeTtHy , 1 < y ≤ 2 (γ-Phasen), zeigen sowohl die Strukturmotive von Einlagerungs- als auch von polyanionischen Hydriden. SrSiH1.6 und BaSiH1.9 als literaturbekannte Verbindungen wurden das erste mal strukturell charakterisiert. Die homologe Reihe konnte um SrGeH1.2 , BaGeH1.6 und BaSnH1.3 erweitert werden. Die Ae4 -Tetraeder sind in diesen Phasen vollständig mit Hydridionen besetzt. Zusätzlicher Wasserstoff bindet kovalent an die Polyanionen. Außerdem verknüpfen sich die Zickzackketten z. T. senkrecht zur Kettenrichtung. Es wurden insgesamt drei Strukturtypen differenziert, die alle strukturell eng verwandt sind. Das führt zu Problemen bei der Strukturbestimmung aus Pulverdaten. Der kovalente Charakter der Bindung wurde durch Festkörperkernresonanzspektroskopie und Dichtefunktionaltheorierechnungen charakterisiert. Typische Tetrel-Wasserstoff-Bindungslängen sind 155(2) pm (Si-H), 163(2) pm (Ge-H) und 186(1) pm (Sn-H). In situ -Neutron, Röntgen- und Synchrotronpulverbeugung wurden angewandt um Reaktionsabläufe aufzuklären. Beim Heizen unter Wasserstoffdruck treten im AeTt-H2 -System (Ae = Sr, Ba, Tt = Ge, Sn) verschiedene reversible Reaktionen zwischen den γ-, β- und α-Phasen auf, bevor ein irreversibler Zersetzungsschritt in die binären Hydride AeH2 und die Tt-reichen Zintl-Phasen AeTt2 beobachtet wird. Ein In situ Beugungsexperiment der Reaktion von NdGa mit Wasserstoff zeigt direkt die Bildung von NdGaH1+x (isostrukturell zu γ-AeTtHy ), das eine Zusammensetzung von mindestens x = 0.17 bis 0.80 aufweist. Die Ga-H Abstände sind lang (ca. 200 pm) und darum keine klassischen 2-Elektronen-2-Zentrenbindungen. In situ Beugung an den Reaktionen von KSi und CsSi mit Wasserstoff konnte gezeigt werden, dass die Hydride KSiH3 und CsSiH3 in einem Schritt gebildet werden. Diese Phasen weisen SiH3--Anionien auf, die isoelektronisch zu PH3 sind. Weiteres Heizen unter Wasserstoffdruck führt zur Zersetzung in KH und K8Si46 oder zur Rückbildung von CsSi. Außerdem wurde eine Reihe weiterer Verbindungen auf die Reaktivität gegenüber Wasserstoff untersucht. Die Phasen AeTt2 , AGe und ASixGe1-x (A = K, Rb, Cs) bilden keine Hydride unter den untersuchten Bedingungen (mindestens 5 MPa H2, 700 K). Die Gallide CaGa, Sr8Ga7 und Ba8Ga7 weisen Reaktivität gegenüber Wasserstoff auf. Diese Beispiele zersetzen sich in binäres Hydrid und die galliumreichen Phasen Ca3Ga8, SrGa4 und BaGa4 . In situ Laborröntgenbeugung der Reaktion von CaGa mit Wasserstoff führt zur Bildung einer neuen, kristallinen Phase. Bildung und Zersetzung laufen in einem sehr schmalen Temperaturfenster ab. Die neue Phase konnte noch nicht charakterisiert werden. / The hydrogenation of Zintl phases leads to interstitial hydrides that are coordinated exclusively by cations, polyanionic hydrides that exhibit a covalent bond to the more electronegative element, or a combination of both motifs. A series of new compounds is prepared and structurally characterised by laboratory X-ray, synchrotron and neutron powder diffraction. Most examples can be derived via hydrogenation of CrB- or FeB-type Zintl phases. These structure types are closely related and characterised by polyanionic zigzag chains. The interstitial hydrides LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) are oxidation products of the formally metallic Zintl phases LnTt = Ln3+ Tt2- e- . Hydrogen occupies tetrahedral Ln4-voids. The products occur as a filled FeB-type phase (P-phase, LaGeH-structure type) or a filled CrB-type phase (C-phase, ZrNiH-structure type). The hydrogenation of electron-precise Zintl phases AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-structure type) leads to hydrogen-poor (AeTtHy , y < 1) and hydrogen-rich phases (AeTtHy , 1 < y ≤ 2). The first show partially hydrogen-filled Ae4-voids. For low contents y < 0.4, hydrogen is statistically distributed over the voids (α-phases). Slightly increased hydrogen contents lead to partial (β-SrGeHy , 0.47 ≤ y ≤ 0.75) or full ordering (β-BaGeH0.5 ). The hydrogen-rich phases AeTtHy, 1 < y ≤ 2 (γ-phases), combine interstitial and polyanionic hydride motifs. The literature-known phases SrSiH1.6 and BaSiH1.9 could be structurally characterised for the first time. The homologue series was extended to SrGeH1.2, BaGeH1.6 and BaSnH1.3 . Tetrahedral Ae4-voids are totally filled with hydride anions. The additional hydrogen binds to the polyanions. Furthermore, some of the zigzag chains are interconnected perpendicular to the chain direction. Three different structure types exhibiting a close structural relationship were identified. This leads to difficulties in structure determination from powder diffraction. The covalent character of the bond is characterised by solid-state nuclear magnetic resonance and density functional theory calculations. Typical tetrel-hydrogen bond lengths are 155(2) pm (Si-H), 163(2) pm (Ge-H) and 186(1) pm (Sn-H). In situ neutron, X-ray and synchrotron powder diffraction were used to elucidate reaction schemes. The AeTt-H2 systems (Ae = Sr, Ba, Tt = Ge, Sn) show several reversible reaction steps between γ-, β- and α-phases upon heating under hydrogen pressure. Finally, an irreversible decomposition into the binary hydrides AeH2 and Tt-rich Zintl phases AeTt2 occurs. In situ diffraction of the reaction of NdGa with hydrogen leads directly to NdGaH1+x (isostructural to γ-AeTtHy ) which shows a large compositional range from at least x = 0.17 to 0.80. Ga-H distances are long (about 200 pm) and, thus, not classical 2-electron-2-center bonds. In situ diffraction of the reactions of KSi and CsSi with hydrogen show a one step formation of the corresponding hydrides KSiH3 and CsSiH3 . They exhibit SiH3--anions which are isoelectronic to PH3 . Further heating under hydrogen pressure leads to decomposition into KH and K8Si46 or reformation of CsSi, respectively. Finally, further compounds were tested for reactivity towards hydrogen. The phases AeTt2 (Ae = Ca, Sr, Ba, Tt = Si, Ge), AGe and ASixGe1-x (A = K, Rb, Cs) do not form corresponding hydrides under the investigated conditions (at least 5 MPa H2, 700 K). The gallides CaGa, Sr8Ga7 and Ba8Ga7 show reactivity towards hydrogen. They decompose into binary hydride and the gallium-rich phases Ca3 Ga8 , SrGa4 or BaGa4. Furthermore, laboratory in situ diffraction of the reaction of CaGa with hydrogen indicates the formation of a new, crystalline phase. Formation and decomposition occur in a relative small temperature window. The new phase could not be characterised, yet.

Contents of major, minor and trace elements in clinopyroxenes and clinoamphiboles of basanites, volcanoclastics, essexites, sodalitic syenites, and monzodiorites of the České středohoří Mts. has been determined using an electrone microprobe and LA-ICP-MS techniques. Composition of clinopyroxenes corresponds to either diopside or augite and clinoamphiboles can be classified as kaersutite or pargasite. Some pyroxenes display pronounced sector zoning showing increased contents of Mg and Si in pyramidal sectors whereas prismatic sectors show Fe, Ti and Al enrichment. Chemical composition of both sectors corresponds to diopside. Growth zoning has been found in the samples from basanites and volcanoclastics. Grain cores display the chemistry of augite and towards the rim the chemical composition changes to diopside. Samples have also been analyzed by powder and single crystal X-ray diffraction techniques. Samples of pyroxenes appear to be either pure or they contain negligible admixtures of phlogopite. Samples of amphiboles are also either without any admixtures or they show contamination by low amounts of diopside or augite, or phlogopite may rarely be encountered. Mutual relationship between the size of the unit cell parameters b and and substitutions in M1,2,3 and A sites has been observed. Longer mean T-O...